CA1080230A - 0-alkyl-0-(6-substituted-pyridazin-(3)yl)-(thiono) (thiol)alkanephosphonic acid esters - Google Patents

Abstract

Abstract of the Disclosure O-Alkyl-O-[6-substituted-pyridezin(3)yl]-(thiono) (thiol)alkanephosphonic acid ester of the formula

Description

108(~;~30 The present invention relates to and has for its ob~ects the Provision of particular new substituted 0-alkyl-0-[6-substituted-pyridazin(3)yl~-(thiono) (thiol)alkanephosphonic acid e~te$s which pos~ess in~ecticidal, acaricidal, nematicidal and fungicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids, nematodes and fungi, with other and further ob~ects becoming apparent from a study of the within specification and accompanying examples.
It is known from U.S, Patent 2,759,938 and German Published Specification DOS 2,049,813 that substituted pyridazinyl-thionophosphoric(phosphonic)acid esters, for example, 0,0-di-ethyl-0-~6-hydroxy-(Compound A) or 6-chloro- (Compound B) or 6-N,N-dimethylcarbamoyloxy-pyridazin(3)yll-thionophosphoric acid ester (Compound C), and from published Netherlands Patent Application 6,904,664 0-ethyl-0-~1,6-dihydro-6-oxo-pyridazin-(3)yll-thionomethane-(Compound D) and ethanephosphonic acid ester (Compound E)~ have insecticidal and acaricidal properties.
The present invention provides, as new compounds, the pyridazinyl(thiono) (thiol)phosphonic acid esters of the general formula R1Y ~ p o~ R (I) R2~ N

Le A 16 565-2-- 1 0 ~ Z 30 in which X and Y each independently is oxygen or sulfur, Rl is alkyl with 1 to 6 carbon atoms, R2 is alkyl with 1 to 4 carbon atoms, R3 is alkoxy with 1 to 4 carbon atoms, alkynyloxy with 2 to S carbon atoms, alkylsulfonyl-oxy with 1 to 3 carbon atoms, monoalkylcarbamoyloxy with 1 to 3 carbon atoms, halogen, benzyl.oxy, benzoyloxy, phenoxy, or phenoxy carrying at least one substituent selected from halogen, nitro, cyano, -S02CH3, -S02CH2Cl, and alkyl, halogenalkyl or alkylthio, each with up to 3 carbon atoms, and R4 ~s hydrogen or alkyl with 1 to 3 carbon atom6.
Preferably, X represent~ sulfur, Y represents oxygen, Rl represents straight-chain or branched alkyl with i 1 to 5 carbon atoms, ~ represents straight-chain or branched alkyl with 1 to 3 carbon atoms, ~ represents straight-chaln or branched alkoxy with 1 to 3 carbon atoms, straight-chain or branched alkynyloxy with 3 or 4 carbon atom~, chlorine, bromine, methylsulfonyloxy, ethylsulfonyloxy, N-methyl-carbamoyloxy or N-ethylcarbamoyloxy, benzoyloxy or benzyloxy or represents phenyloxy which preferably carries one, two or three ~ubstituents selected from chlorine, nitro, cyano, methyl, ethyl, methylthio, ethylthio and trifluoromethyl, the substituent~ not necessarily being identica~ in the case of di- or trisubstitution, and R4 represents hydrogen, ~ethyl or ethyl.

Le A 16 565 -3-.
.. . . . .

Surprisingly, the pyridazinyl(thiono)(thiol)phosphonic acid esters according to the invention show a better insecti-cidal, acaricidal and nematicidal action than the corre~pondiu known substituted pyridazinylthionophosphoric(phosphonic) acid ester~ of analogous structure and of ths same type of action.
The products according to the preæent invention thu~ repreeent a genuine enrichment of the art.
The present invention also provides a process for the preparation of a pyridazinyl(thiono)(thiol)pho~phonic acid ester of the formula (I) in which (a) a (thiono)(thiol)pho~phonic acid ester halide of the general formula ~ 1 ~ P-Hal (II), ., R2 in which R1, R2, X and Y have the above-mentioned meanings and Hal repre~ents halogen, preferably chlorine, is reacted with a l,6-dihydro-6-oxo-pyridazine derivative of the general formula R~ ~ -0 (III), in which R3 and R4 have the above-mentioned meaning, if appropriate in the presence of an acid acceptor or, if appropriate in the form of a corresponding alkali metal salt, alkaline earth metal salt or ammonium salt, and optionally in the presence of a solvent, or (b) provided that a compound of the formula (I) in which Le A 16 565 -4-represent~ alkylsulfony1oxy or benzoyloxy iB required, a pyridazinyl (thiono)(thiol)pho~phonic acid e~ter of the general formula H0 ~ 0-P \ (IV), in which R1, R2, R4, X and Y have the above-mentioned meanings, is reacted with an acyl halide of the general formula R5Hal2 (V), in which R5 repre~ents alkyl~ulfonyl with 1 to 3 carbon atoms or benzoyl, and Hal2 repre~ents hslogen, preferably chlorine, ii appropriate in the presence oi an acld acceptor and, 1 appropriate, in the presence oi a solvent, or (c) provided that a compound oi the iormula (I) in which R3 represents monoalkylcarbamoylo~y i8 required, a compound oi the formula (IV) is reacted with an alkyl isocyanate oi the general formula Alk-NC0 (VI), in which Alk repre#ents alkyl with 1 to 3 carbon atoms, ; if appropriate in the presence oi a cat lyst and, ii appro-~ priate, in the presence of a sol~ent.
:
:

` Le A 16 565 -5-.

If, ior esample, ~ollowlng proce~e variant (a), 8-ethyl-thiolethanepho~phonic acid chloride and 3-hydro~y-6-N-ethyl-carbamoylo~ypyridazine are u~ed, or iollowing proce~s variant (b), O-ethyl-0-~6-hydro~y-pyridazin(3)yl]-n-propanepho~phonic acid die~ter and benzoyl chloride are used, or iollowing proce~s variant (c), O-ethyl-0-[6-hydrosy-pyridazin(3)yl]-thionoethanepho~phonic acid e~ter and ~thyl isocyanate are uced a~ the starting material~, the cour~e o~ the reaction can be repre~ented by the iollowing equationc:

( ) C H S ~ _o-co-NH-c2H5

2 5 (IIa) (IIIa) Acid-bl~ding C H /P ~ C2H5 (b) C2H90~p o ~ -OH + Cl-C

(IVa) (Va) C2H5 ~P-Og~h-(c) C2H50 ~ p_o ~ -OH + C2H~_NCO -~~~~~
C2 5 (IVa) CVIa) 2H5 / P- ~- N C2H5 (60) Le A 16 565 -6-, ~, .

The (thiono)(thlol)phoephonlc acld ~eter halideu (II) and pyridazinyl(thiono)(thiol)phoephonic acld ecter~ (IV) to be u~ed a~ ~tarting materlale are known and oan be prepared in accordance wlth cuetomary proce~eee (~ee, ~or e~ample, U.~.Patent ~peciflcatlon 3,167,574, Belglan Patent Speci-ficatlon 671,91~ and Netherlande P~tent Applicatlon 6,904,664).
The following may be mentioned a~ ~peci~lo examples:
0-methyl-, 0-ethyl-, 0-n-propyl-, 0-ieopropyl-, 0-n-butyl-, 0-isobutyl-, 0-sec.-butyl-, 0-tert.~butyl- and 0-n-pentyl-methane-, ethane-, n-propane- and leopropane-phosphonlc acld ester chlorldee and the correepondlng thlono analogue~;
S-methyl-, S-ethyl-, 3-n-propyl-, S-leopropyl-, S-n-butyl-, S-lsobutyl-, S-eec.-butyl-, ~-tert.-butyl- and S-n-pentyl-methane-, ethane-, n-propane- and ieopropane-thlolphosphonlc acid ester chloridee and the correepondlng thlono analoguee;
0-methyl-, 0-ethyl-, 0-n-propyl-, 0-i~opropyl-, 0-n-butyl-, 0-isobutyl-, 0-eec.-butyl-, 0-tert.-butyl- and 0-n-pentyl-0-[4- or 5-methyl-6-hydroxypyridazin(3)yl]-methane-, ethane-, n-propane- and isopropane-phosphonic acid e~ters and the corresponding thiono analogue~; 0-methyl-, 0-ethyl-, 0-n-propyl-, 0-isopropyl-, 0-n-butyl-, 0-isobutyl-, 0-~ec.-butyl-, 0-tert.-butyl- and 0-n-pentyl-0-[6-hydroxypyridazin(3)yl]-methane-, ethane-, n-propane- and isopropane-pho~phonic acid esters and the corresponding thiono analogues; and S-methyl-, S-ethyl-, S-n-propyl-, S-isopropyl-, S-n-butyl-, S-isobutyl-, S-sec.-butyl-, S-tert.-butyl- and S-n-pentyl-0-~6-hydro~y-pyridazin-

(3)yl]-thiol-methane-, ethane-9 n-propane- and isopropane-phosphonic acid ester~, the corresponding thiono P~nlogues and, in each case, the compounds substituted by methyl in the pyridazine ri~B in th~ 4- or 5-poeition.

Le A 16 565 -7-~080Z30 3-Hydroxypyridazine der~vatives (III) are known snd they can be prepared in accordance with customary processes, for example, if R3 represents alkylsulfonyloxy, by reacting the known 1,6-dihydroxypyridazine with alkylsulfonic acid halide. For further processes for the preparatlon of the known 3-hydroxypyridszine derivatives (III) see, for ; example: T, Jo~ima and Takeshiba, Agr Biol. Chem. 38, 1169-1176 (1974); T. Nakagome, Yakugaku Zas~hi, 82, 1005 (1962), J. Druey, K. Mkier and K. Eichenberger, Helv. Chim.
Acta 37,-121-133 (1954) and Belgian Patent Specification 813,225.
The followlng may be mentioned as ~pecific example~:
6-chloro-, 6-bromo-, 6-methylsulfonyloxy-, 6-ethylsulfonyloxy-, 6-methoxy-, 6-ethoxy-, 6-n-propoxy-, 6-isopropoxy-, 6-propargyloxy-, 6-N-methyl-carbamoyloxy-, 6-N-ethyl-carbamoyloxy-, 6-benzyloxy-, 6-benzoyloxy-, 6-(2-nitro-4-trifluoromethylphenyloxy)-, 6-(2,4-dichlorophenyloxy)-, 6-(2,5-dichlorophenyloxy)-, 6-(2,4,6-trichlorophenyloxy)-, 6-(2-methylthiophenyloxy)-, 6-(2-ethylthiophenyloxy)-, 6-(4-methylthio- and 4-ethylthiophenyloxy)-, 6-(2-nitro- and

4-nitro-phenyloxy)-, 6-(4-cyanophenyloxy)-, 6-(2- and 4-methyl- and -ethyl-phenyloxy)-, 6-(2,4-dimethylphenyloxy)-, 6-(2,4-diethyl-phenyloxy)-, 6-(3-methyl-4-methylthiophenyloxy)-; and 6-(3-ethyl-4-methylthiophenyloxy)-3-oxo-pyridazine and the corresponding derivati~es which are substituted by methyl or ethyl in the 4- or 5-position in the pyridazine ring.
The acyl halides (V) and the alkyl i~ocyanate~ (VI) are known and can be prepared in accordance with generally customary proce~se~ described in the literature.
':

Le A 16 565 -8-.~

108f3Z30 The following may be mentioned specifically as examples of these compounds: methylsulfonyl chloride, ethylsulfonyl chloride and benzoyl chloride, and methyl isocyanate, ethyl iso-cyanate, n-propyl isocyanate and isopropyl isocyanate.
The process variants (a) to (c) for the preparation of the compounds according to the invention are preferably carried out in the presence of suitable solvents and diluents.
Practically all inert organic solvents can be used for this purpose, especially aliphatic and aromatic, optionally chlorinated, hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxane; ketones, for example acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone;
; and nitriles, such as acetonitrile and propionitrile.
All customary acid-binding agents may be used as acid acceptors in process variants (a) and (b).
Alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate and potassium carbonate, sodium methylate and ethylate and potassium methylate and ethylate, have proved particularly suitable, as have aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethyl-amine, dimethylaniline, dimethylbenzylamine and pyridine.
Process variant ~c) can optionally be carried out in the presence of a catalytic amount of a tert. organic base, for ., example diazabicyclooctane or triethylamine.
In all process variants, the reaction temperature can be varied within a substantial range. In general, the reaction is carried out at between 0 and 120C, preferably at from 10 to 60C.
:' , _ g _ ~he reaction i8 in general allowed to take place under normal pres3ure.
To carry out variant~ (a) and (b), the reactants are preferably employed in equimolar amounts. An excess of one or other component produces no significant advantages. In proce~s variant (c), the alkyl isocyanate component is preferably added in 10 to 15% e~ce~s.
In all variants, the reaction is in general carried out in one of the above-mentioned solvents at the stated temperatures. After completion of the reactlon, the batch can be worked up a~ described below. In procees varlant (a) the reaction mixture is filtered and then poured lnto an organic 301vent, and the organic layer is worked up in the usual manner, while in process variants (b) and (c) the reaction solution is worked up directly, for esample by washing, drying and ~tripping of~ the solvent, or by directly distilling off the latter.
The new compounds are mo~tly obtained in the form of oils, which frequently cannot be di~tilled without decomposition, but are freed from the last volatile oonstituent~ by so-called "slight distillation", that is to say by prolonged heating under reduced pressure to moderately elevated temperatures-, and are purified in this way. They are characterized by the refractive index. Some of the compounds are obtained in a crystalline form; the~e are characterized by their melting points.

Le A 16 565 -10-~08VZ30 As already mentioned, the pyridazinyl(thiono)(thiol)-phosphonic acid ester~ according to the invention are dis-tinguished by an excellent insecticidal, acaricidal and nematicidal activity. They are active against plant pests, pests harmful to health and pests oi stored products and combine a low phytotoxicity with a good action against both sucking and biting insects and against mites; most oi the compounds furthermore exhibit a fungicidal action.
For thi~ reason, the compound~ according to the invention can be employed successfully as pesticide~ in plant protection and also in the hygiene field and the iield of protection o~
stored products.
To the sucking insect~ there belong, in the main, aphids (~phididae) such as the green peach aphid (~YZU9 per~icae), the bean aphid (Dorali~ ~abae), the bird cherry aphid (RhopalosiPhum Padi)~ the pea aphid (Macrosiphum PiBi) and the potato aphid (Macrosi~hum ~ol ni~olli), the currant gall aphid (Cr~tomvzus korechelti), the rosy apple aphid (~aPPa~his mali), the mealy plum aphid (HvaloPterus arundini~) and the cherry black-ily (MYZW cera~1); ln additlo~, ~cale~ and mealybues (Coccina), for example the oleander scale (A~Pidio-tus hederae) and the soit scale (~ecanium hesPeridum) as well as the grape mealybug (Pseudococcus maritimus); thrips (Thysano~tera), such as HercinothriPs iemoralis, and bugs, ior example the beet bug (Piesma quadrata), the red cotton bug (Dvsdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius Prolixus) and Chagas' bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus.

Le A 16 565 In the ca~e of the biting in~ect~, above all there ~hould be mentioned butterfly and moth caterpillars (~
doptera) such as the diamond-back moth (Plutella maculiPennis), the gyp8y moth (Lvmantria disPar), the brown-tail moth (EuProcti~ chr.vsorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mame~tra brassicae) and the cutworm (A~rotis se~etum), the large white butter~ly (Pieris brassicae), the ~mall winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (~aPh.Y~ma fru~iperda) and cotton worm (Prodenia litura), the ermine moth (XYPonomeuta Padella), the Mediterranean flour moth (EPhestia kuhniella) and Breater wax moth (Galleria mellonella).
Also to be classed with the biting insects are beetles (Coleo~tera), ior example the granary weevil (SitoPhilus ~ranarius = Calandra Rranaria), the Colorado beetle (~ePtino-tarsa decemlineata), the dock beetle (GastroPhv~a viridula), the mustard beetle (Phaedon cochleariae), the blo~om beetle (MeliRethes aeneus), the raspberry beetle (BYturus tomentosus), the bean weevil (Bruchidius = Acantho~celides obtectus), the leather beetle (Derme~tes ~ri~chi), the khapra beetle (~ro~o-derma Rranarium), the flour beetle (Tribolium caetaneum), the northern corn billbug (Calandra or Sitophilus zeamal~), the drug~tore beetle (Ste~obium E~iceum), the yellow mealworm (~enebrio molitor) and the saw-toothed grain beetle (Or.vzae-; p;hilus surinamensis), and also species living in the soil, ~or e~ample wireworms (A~iotes ~pec.) and larvae o~ the cock-Le A 16 565 -12-108~)230 chafer (Melolontha melolontha); cockroaches, such as the ~erman cockroach (Blattella ermanica), American cockroach (Periplaneta Americana), Madeira cockroach (~eucoPhaea or RhvParobia maderae), oriental cockroach (~latta orientali~), the giant cockroach (Blaberus ~i~anteus) and the black giant cockroach (Blaberus ~U8CU~) as well as Henschoutedenia ~lexi-vitta: further, OrthoPtera~ for e~ample the house cricket (~rvllus domesticus); termites such as the ea~tern sub-terranean termite (Reticuliterme3 flavi~es) and XYmeno~tera such as ant~, for example the garden ant (Lasius ni~er).
~ The DiPtera comprise e~sentially the ilies, such as the vinegar fly (DrosoPhila melano~aster), the Mediterranean fruit ily (Ceratitis ca~itata), the house ~ly (Musca dome8tica), the little house ~ly (Fannia canicularis), the black blow fly (Phormia re~ina) and bluebottle ily (Calli~hora erYthroce~hala) as well as the stable ily (Stomo~Y~ calcitran~ urther, gnats, for example mosquitoes such a~ the yellow fever mo~quito (Aede ae~vti), the northern house mo~quito (Cule2 i~iens) and the malaria mo~qulto (Ano~helo~ ste~hen~i), With th0 mite~ (Acarina) there are classed, in particular, the spider mites (Tetran~idae) ~uch as the two-spotted spider mite (~etr_~chus urticae) and the European red mite (Para-tetra~Ychue ~ilosus = Pano~chus l-lm~)~ gall mites, ~or e~ample the blackcurrant gall mite (Erio~hre~ ribis) and tar~o~emid~, ior esamplo th~ ~road mite tHomit~r~onomus latus) :, Le A 16 565 -13-iO8V230 and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick ~Ornithodorus moubata).
When applied against pests harmful to health and pests of stored products, particularly flies and mosquitoes, the process products are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.
The active compounds according to the invention couple a low toxicity to warm-blooded animals with powerful nematicidal properties and can therefore be used to combat nematodes, especially phytopathogenic nematodes. These essen-tially include leaf nematodes (Arphelenchoides), such as the chrysanthemum eelworm (A. ritzemabosi~, the leaf-blotch eel-worm (A. fragariae) and the rice eelworm (A. oryzae); stem nematodes (Ditylenchus), such as the stem eelworm (D. ~
root-knot nematodes ~Meloidogyne), such as M. arenaria and M. incognita; cyst-forming nematodes (Heterodera), such as the potato cyst eelworm (H. rostochiensis) and the beet cyst eel-worm (H. schachtii); and also free-living root nematodes, for example of the genera Pratylenchus, Paratylenchus, Rotylenchus, Xiphinema and Radopholus.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesti-cide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert or-ganic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, - 15 _ .

.

~08~230 especially chlorinated, aromatic hydrocarbons (e.g. chloro-benzenes, etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), - chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols ~e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.~, sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or ~; water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, .e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the follow-ing may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, : methyl cellulose, etc.

~81~230 Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides, nematicides and fungicides, or bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
; As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-95% by weight, and preferably 0.5-90% by weight, of the mixture, whereas car-rier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10%, preferably 0.01-1%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as ~1) a dispersible inert finely divided carrier solid, and/or ~2) a dispersible carrier liquid such as an inert organic solvent and/or ~:
:.

water, preferably including a surface-active effective amount of a carricr vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.01-95%, by weight of the mixture.
The active compounds can also be used in accor-dance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid composi-tions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.
When used against nematodes, the preparations are generally applied to an area of agriculture in amounts of 1 to 100 kg of active compound per hectare, and are then incorporated into the soil.

Furthermore, tlle present invention contemplates methods of selectively killing, combating or controlling pests, e.g, insects, acarids, nematodes and fungi, and more particularly methods of combating insects, acarids and nematodes, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (c) such nematodes, (d) such fungi, and (e) the corresponding habitat thereof, i.e. the locus to be protected, e.g. to a growing crop, to an area where a crop is to be grown or to a domestic animal, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally, nematocidally or fungicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied . ., in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrusting, and the like It will be realized, of course, that the concen-tration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application, Therefore, in special cases it is ` possible to go above or below the aforementioned concentration ranges.
; 25 The unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

~08V230 Example 1 DrosoFhila test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emul-sifier, and the concentrate was diluted with water to the desired concentration.
1 cm3 of the preparation of the active compound was applied with a pipette to a filter paper disc of 7 cm diameter.
The wet disc was placed over the orifice of a glass vessel containing 50 vinegar flies (Drosophila melanogaster) and covered with a glass plate.
After the specified periods of time, the destruc-tion was determined in %. 100% means that all the flies were killed; 0% means that no flies were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table:

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,: . ' ' , " . . : -' ~080230 Exam~le 2 Phaedon larvae test -- ~.
~olvent: ~ part~ by weight of acetone Emulsifier: l part by weight of alkylaryl polyglycol ether To produce a ~uitable preparation o~ active compound, 1 part by weight of the active compound was mi~ed with the stated amount of solvent containing the stated amount o~
emuleifier and the concentrate wa~ diluted with water to the : desired concentration.

Cabbage leaves (Brassica oleracea) were sprayed with the preparation o~ the active compound until dripping wet and were then infested with mustard beetle larvae (Phaedon cochleariae).

After the ~pecified periods o~ time, the degree of destruction wa~ determined in ~: 100% mean~ that all beetle larvae had been killed whereas 0% means that none o~ the beetle larvae had been killed.

~he active compounds, the concentrations oi the active compounds, the evaluation times and the rssults can be seen , 20 from the i'ollowing table:
: .
' Le A 16 565 - 25 _ 0 ?

11;)8(3230 I

!

o .~
y h O U~
00 oo 00 00 ~ O O 0 00 o ~ _ _ _ _ a~
~I h ~) 4D~
a~

~ O O O 0 0O 00 . .. .. .

,1 P rl

5~ ~ ~
~d ~
E~ O

:C~ O
V \/
. ~ ~ O

.P ~ :~
~: C~

I.e A 16 565 _ 21; -- '. . ~ . ' .,~
o h h ~d ~d t"
~ hg 0 g g g 0~ 8 g a) ~ _ , , ,. _, h~

S:: -- O
O ~ C~
, ~ P~'~ o _ O _ O~
~ rl O O O O 0 0 0 ,' ~1 ~1 a) n~
~ ~O ~ h cd ~ ~ ~
,,' ~ '¢O

~ ,~
. 0~ ~ _ ~

T t ~P. ~ ¢~
.~ ~

,~
m ~ o u I,e A 16 565 - 27 -æ

.~
o ,~
c~
y a~ tq ~ ~d o o O O O
.. a a~
~d bD
.,, u~
o a c~
a 1~
I,~ ~de ~o ~o _o ~o ~o p~ o o. o o. o o. o. o l ~o oo oo oo oo ~, o -.~ _ O ~ ~
~ u~
_ -- ~ o ., :~ ~ r~
~. ~ u~ p~
v ~ u~ u~
o v ~ ~
\ / ~ v ~ ~ ~ l Le A 16 565 - 28 , O
.,~
.

o\o o 1080Z~0 o o O o O O O O
O ~
h h ~d . ~

8 '' ~, ~, ~
_, ~ ~ o\O
~ ~ ~o.~ ~ ~ .
~o ~o ~ ~ oo oo c~ ~1 rl O O
--' l .dl ~ ~
E~ ~1 ¢"

:

., ~ ~

Vl .,, ,. .,, ~

o 3 \ /
. \ / o U~ - P., 1 f~, ~

- - : .
' ~080Z30 ~xamPle ~ ;
~lutella te~t ~;
Solvent: 3 parts by weight of acetone ~mulsifier: 1 part by weight of alkylaryl polyglycol ether . To produce a ~uitable preparation oi active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the ~tated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillar~ oi the diamond-back moth (Plutella maculi~enni9).

Aiter the specliied periods oi time, the degree oi destruction was determined a~ a percentage: 100% means that all the caterpillars were killed whereas 0~ means that none of the caterpillar~ were killed.

The active compound8, the concentration~ oi the active compounds, the evaluation timee and the result~ can be seen irom the iollowine table:

~:;

~e A 16 565 -30 -. ~ . . . .

r1 U~
a) u~
~ ~ 8 ~ 8 8 8 8 o 8 o o ~ . . . ~ . ~ ~
~ h tl~) J' a~ tH

':

C) o , ~ ~ .
o o . o 8 _ o o ~ o 8 ~ o o , ~ ~ ooo ooo ooo ooo u~ P h a) ~ ~ ~
~d ~1 _ --' N

O ~ u, ~ ,~ ~r 'nO

~ Çj Ç~

I,e A 16 565 _ 31-i ooo ooo ooo ooo o~ ooo ooo ooo ooo ~ _ _ _ _ __ _ _ _ _ _ a~
~ h bD
~H
cd , ~d ,a ~ O
~0~

~ P O O _ O O - -,~ ~ O O 000 000000 000 ~1 ~1 ~
~ ~ r~ q td ~ ~C~
.. ~ ~
:: ~ ~ _ ~_ _ _ W~ WN

yN I, ~N

0~ ~ o~ U

~ -I V
¢

Ie A 16 565 _ 32 _ ~108V230 o\

.
~, V~
ooo o o .,. o o o o o o oo o ~ o o o ~ ~ _, C~
a) h h a ~:s ': o ~
~-- ~ ~ 0\o C~ O ~~
a) ~d ~ O ~ O _, o o ~ O O
~ ~ ~.oOo 000 000 D ~ ~ h .` ~d E- ~ ~C

o L~

V) .~

\ / \ / U~\C/
V~ _ G o O O
:~ ~ [~

Example 4 ~y~ test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concen-tration.
Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (~y~ persicae) were sprayed with the preparation of the active compound until dripping wet.
After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the aphids were killed whereas 0% means that none of the aphids were killed.
The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table:

:

.

. 1080230 o~o o o o o o oo o o o o o o o o o o o o~ o o o o o oo o a h C~
~4~

o ,_ ~
o\ ~ O ~ O ~ O _~ O
_l O o ~ o o ~ o o _l I~' OoO oOO Ooo ooo E- ~
.~ ~
~) o '; ¢~

.

~ ~ ~
~_ .
,_ . o~ O ,' ~ rl O
.:,, ~ 1~ ~rl U) ,:' ~ O ~ t~
'. :C \ / \ /
, ~ ~ ~ o X U~ _ X ~ C \ O U~

:, ¢
¢ o .,, .. o rl ~q ~, ~:1 h ~d 00~ ooc~ ooo ooa~
o 00~ ooa~ oo~ oocr _ _ _ _ _ _ _ . _ a) ~) h S~
qD~
~1) ~ ~d :, ~ o .` ~ ~'~
0 -~1 O ~:4 ,~ _ o O . O _ O _ _ O
-;. t,,, _oo _oo _o8 _oo .' ~ ~ ~ h` 000 000 000 000 .~ 6q ., a~ ~
~ ~ C~ _ _ _ _ .~
O
.~, ~
0~ ~

~ 8 1~ /

Le A 16 565 _ 36 _ 108()230 .

a ,~

o~
'd h 8' ~ ' q~ 0~ oga~ ooo ooa~
o _ _ _ . _ _ _ _ a~ h h bO~
cd :: ~ 8 .

_o _o _oo _o _ ~ ... ... ... ...
~ ~ ~ ooO oOo 000 ooo a~ a~ ~ ~
~. i, ~1 ~ , ^ I~ N -- u~

U~ X~
u~ N m N
,) N ~ U O

~0 ~

~e A 16 565 -37 -~R
,~
,~, h m ~d OoO ooa~ ocr~o~ OOu~ 00 o o o a~ o o a~ o cr~ a~ o o o~ O O
a) a~ h h ~D~
a :' ~

c~ o ~ c~
~ _ ~
. m o.
a) a) P~
~ m o .,~ _ o o ; ~ O O . 0 0 - O 0 --,D N ~ O O O O O O oO O O o O O O O
~; ~

u~

' u~
_ o ~ P ~ Q

I.e A 16 565 - 38 -~080230 ~xamPle 5 Tetranychus test (resi~tant) Solvent; 3 parts by weight of acetone ~mulsifier: 1 part by weight o~ alkylaryl polyglycol ether To produce a suitable preparstlon of active compound, 1 part by weight of the active compound was mixed with the stated amount o~ solvent contalning the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

`~ 10 Bean plants (Pha~eolus vul~aris), which had a height of approximately 10-30 cm, were sprayed wlth the preparation , ., of the active compound until dripping wet. These bean plants were heavily infested with the two-spotted spider mite (~etranvchus urticae) in all stages of development.

After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the spider mites were killed whereas 0~ means th~t none o~ the spider mites were killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following table:
.

~e A 16 565 -39 -,~
rl h U~
~ ~ ~ o u~o u~o 8 a) ~> h h b a) q~

,~.
o~ ~
oo oo oo oo E~

~ In In r~ ' ~ ~ 8 \ /

Le A 16 565 - 40-.~

r~

Ul a~ a~
~ oo 00 0 o a~
a) a~ h h a bn ' a~ ~H

O
C) ~'~
C~ --_ ~ P~
. u~` a E~ --O --O _ O _ O

~ u~ a~

U~
U N
O U
\ / 3 rn: P~ U N 1 U~
U) I O U

~ \ ~

~ o ~ ~Z ~ h .~ I Jr~ aO ~ 0~
~ u U u ~:

Ie A l 6 565 _41 _ ,~
r~
h ~ ~ 8 0 o 8 8 a~
o a) a) h h a>
~ ld :

a -- ~'~
O ~ ~
.' _ Q) O~r :, ~I P ~ 00 00' 00 00 E~ ~1 ~ ~ C~J -U~
N :1:
U
O O U~

~, ~ ~ C
U ~ U

I.e A 16 565 _ 42_ o ,, o ~ ~ o o o o o~ 8 ~

o a~
~ h h a bD~

.~ I
o o ^ o ~ ~d`~
u~ o-~
~ oo .0 -O .0 -O
,1h o O O O o O o O O

E~ E~ ~o O O ~

~ o X ~ I ~

\ / U~
O

~e A 16 565 - 43 -108()230 a a X
~ h ~d Qa~ oa~ oo q~ o a~ o o~ oo o o N
a~
h a bD~
a~

, ~
, o~
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a~ I ~ a _o o _o . o . ~ e ~ ~ oo oo oo oo .
~: _ _ ~
~ ~ _ ~ U~ o Ie A 16 565 - 44 -`o~

...
h a) u~
~ o~ æ~ oo oæ

~ 5 h b~

C) I
~0 U~ ~ ~` .

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E~ +' l _ C) ~
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O

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~e A 16 565 -45 _ , :

lOt30Z30 o +, a~ ~ 8 8 8 a~ 8 8 a~ h ---- -- __ h bD~
~ ~d rl .' O ~
C) O
a ~ æ
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o E~ +' :' ~ ~C g ~ ~_ -- _ o~ _ ~ ~ O O

o D ~ o '' i ~L T ;~

I.e A 16 565 _ 46 _ : -`

Example 6 1080230 Critical concentration test/soil insects Test insect: Phorbia antiqua grubs in the soil Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concen-tration.
The preparation of active compound was intimately mix-ed with the soil. The concentration of the active compound in the preparation was practically immaterial, the only decisive factor being the amount by weight of active compound per unit volume of soil, which is hereinafter quoted in ppm (= mg/l).
The soil was filled into pots and the pots were left to stand at room temperature.
After 24 hours the test insects were introduced into the treated soil and after a further 2 to 7 days the degree of effectiveness of the active compound was determined in % by counting the dead and live test insects. The degree of effectiveness was 100% if all the test insects had been killed and was 0% if exactly as many test insects were still alive as in the case of the untreated control.
The active compounds, amounts used and results can be seen from the table which follows:

T a b l e 6 Critical concentration test/~oil insects (Phorbla antiqua grubs in the 90il) Active compound Degree of destruction in ~ at an active com-pound concentration of 20 p~m 2 5 \ ~ 0 ~ P-- N~N

(known) (B) o= ~ o_p ~ O0 5 0 ; (known) (E) . Cl S

Cl ~ 0 ~ 0-P ~ H5 (37) 100 Cl ~ 0 ~ O_p ~3~7~1 100 ,S,,OC3H-iso 100 3 ~ ~ 3 3 ~ 0 ~ 0 P~C2p5 (41) lO0 ~ 2 5 CH3-0- ~ -O~P ~ (15) 100 Ie A 16 565 _ 48 _ T a b 1 e 6 (continued) Critical concentration test/soil insects (Phorbia anti~ua grubs in the 80iI) Active compound Degree oi destruction in % at an active com-. pound concentration ; of ?O ~m ' F3C-(~o (~ ,, ~ C2H5 S OC3H7_i90 Cl ~ ~P `CH (18) 100 Isomer mixture CH

. ~ S~ C2H5 (19) 100 : Isomer mixture '. ' S ~oc3H7-l~o CH30- ~ ~
:: N - N CH3 .: .
:~ (2) . : ~ " ~ OC3H7-n . C2H5 ~ (20) ~ . .

L S DC3H7-iso C2H5 (21) I~omer mlxture . ~ .
- -:
:

' . Le A 16 565 _ 49 _ ' T a b 1 e 6 (contlnued) Critlcal concentratlon teet/soll insecte (Phorbia antlqua grube in the eoll) Actlve com~ound Degree of deetructlon ln ~ at an active com-pound concentratlon _ _ __ o~ 20 ~m _ _ " ~ OCH3 3 ~ ~ (22) loo iso-C H 0-~ 0 P~ 2 5 100 (23) S ~ OC3H7-~so iso-c3H o ~ -o-P ~ 100 . (24) -CH2-- ~ -o P ~ 2 5 ,, C2H5 (25) -CH2-- ~ CH3 t26) , " ~ OC3H7-n ~ Cl- ~ -O-P ~ (6) 100 ,; 2 5 ~ ~ 2 5 CH -S02-0 ~ ~ -o-p(12) 100 ' Le A 16 565 - 50 -:
. ' ' .

T a b l e 6 (continued) Critical concentration test/soil lnsects (Phorbia antiqua grubs in the ~oil) Active compound Degree oi destruction in % at an active com-pound concentration of 20 PPm " ~ C4Hg-190 C~ >-o-P ( 1 4 ) 1 00 N-N~ 2 5 " C)C 2 H 5 C2 H 50~ -0-p l 00 (28) /==~ ~ 3 C2H50~ ~)_o_p ~ 100 (30) ~xamPle 7 Critical concentration test/eoil insects Test insect: ?enebrio molitor larvae in the soil Solvent: 3 partq by weight of acetone Emuleiiier: 1 part by weight oi alkylaryl polyglycol ether To produce a suitable prep~ration oi active compound, l part by weight of active compound wa~ mixed with the etated amount oi sol~ent, the stated amount of emuleiiier was added and the concentrate was diluted with water to the desired concentration.
; Ths preparation of active compound wa~ intimately mixed : with the 80il. The concentration oi the active compound i~
the preparation wae practically immaterial, the only deci~i~e iactor being the amount by weight oi acti~e compound per unlt ~olume of 80i~ which i8 quoted hereinaiter in ppm ( = mg/l).
Le A 16 565 - 51 _ 10802~0 The 80il waB illled lnto pots and the pots were leit to stand at room temperature.
After 24 hours the test insecte were introduced lnto the treated ~oil and a~ter a further 2 to 7 daye the degree of e~fectiveness of the active compound was determined in by countin~ the dead and live test insects. The degree of eifecti~eness was 1007~ i~ all the test insects had been killed and was 0~ i~ exactly as many test insects were still alive as in the case o~ the untreated control.
The active compounds, amounts used and results can be seen from the table which follows:
T a b `l e 7 Critical concentration te~t/soil insects (Tenebrio molitor larvae in the 90il) Active compound Degree oi destruction in % at an active com-pound concentration o~ 5 PPm ` ~ ,,/ 2 5 =~ f, -P--OC2H5 (known) (E) ,;, .

CH30- ~" ~ oc3H7 n ( 0) 100 1 S OC3H7-iso Cl ~ 0-P -CH3 (18) 100 Isomer mixture S~OC2H5 ~80-C3H70- ~ C2H5 100 Ie A 16 565 - 52 -T a b 1 e 7 Critical concentration test/soll inaecta (Tenebrio molitor larvae in the ~oil) Active compound Degree o~ destruction in ~ at an active com-pound concentration _ oi ~ ~m i~0--C3H7_0~ n ~ OC3H7 1AO 1 00 C~ 3 (24) ,, ~OC4Hg_i~o C 1-~ ~C2~5 100 S OC H
I 2 51~ OP~ (20) 100 .1 E~am~le8 Critical concentration test/nematodes Test nematode: Meloido~Yne ~3f~LLb~
Solvent: 3 parts by weight oi acetone Bmulsifier: 1 part by weight Or aIkylaryl polyglycol ether To produce a suitable preparation oi active compound, 1 part by weight oi active compound was mi~ed with the stated amount of solvent, the ~tated amount oi emulsliier was added and the concentrate was diluted with water to the desired concentration.
The preparatlon oi actlve compound wae lntimately mised with 8011 which Wa8 hea~ily inie~ted with the te~t nematodes.
The concentration of the acti~e compound in the prep~ration ~aB 0~ practically no import~nce; only the amount oi active compound per unit volume oi ~oil, which ie given hereinaiter ~e ~ 16 565 _ 5~ _ ln ppm, wa~ decisive. The soil wa~ iilled into pot~,lettuce wa~ 80wn in and the pots were kept at a greenhouse temperature o~ 27C.
A~ter 4 weeks, the lettuce roots were e~amined ~or infestatlon with nematodes (root galls), and the degree of e~fectivene~ of the active compound Wa9 determined as a per-centage. The degree o~ e~ectivene~s was 100% when in-festation was completely avoided; it was 0~ when the in~estation was exactly the ~ame as in the case oi the control plants in untreated soil which had been infested in the same manner.
The active compound, the amounte applled and the re~ults can be seen irom the ~ollowing table:
T a b l e Critical concentration tset/nematode~
(Meloido~vne inco~nita) l Active compound Degree oi de3truction in ~ at an active com-pound concentration o~
20 PPm I S CH
Q~-:P--W2H5 o (known) (D) " ~ 2 5 0 ' II OC2H5 (known) tE) S
3 2 0 ~ -0-P(OC2H5)2 0 (known), tc) Le A 16 565 - 54 _ T a b l e 8. (continued) Critical concentration test/nematodes (Meloido,rvne inco~nita) Active compound Degree o~ de~truction in ~ at an active com-pound concentration of 20 p~m 3 ~ 2H5 3 ~ OC H
~+ ~ " ~ 2 5 Cl ~ _~ ~ ~P ~C2H5 Isomer mixture S ~ oc3H7-n CH30 ~ -O P ~ (20) 100 S/ OC3H7-iso Cl~\ / ~ ~P ` C (21) 100 Isomer mixture : n ~ 4 9 ~90 Cl ~ ~C2H5 (14) 100 ~c~ S ~ C)C 2H5 C2H50 ~ C2H5(28) 100 .~ .

S~ OC 2 H5 180-C3~17-~ -P~

(23) Le A 16 565 - 55 -xam~le q LTloo test for Diptera Test insects: Aedes ae~vPti ~olvent: Acetone 2 parts by weight of active compound were dissolved in 1,000 parts by volume of ~olvent. The solution ~o obtained was diluted with further solvent to the desired lower concentrations.

2.5 ml of the ~olution of active compound were pipetted into a Petri dish. On the bottom oi the Petri dish there was a filter paper with a diameter oi about 9.5 cm. The Petri dish remained uncovered until the solvent had com-' pletely evaporated. ~he amount oi active compound per m of filter paper varied with the concentration oi the solution of active compound. About 25 test ineect~ were then placed in the Petri dish and it was covered with a glass lid.

The condition oi the test insecte was continuously observed. The time which was necessary ior 100~ destruction was determined.

The test insects, the active compounds, the concen-tratlons oi the active compounds and the times at which there was 100% destruction can be 9een irom the iollowing table:

.

~e A 16 565 -56 _ ~0 ~ ~
~ 0 ~o ~
3 ~ ll ll 0 m h o 0~ 00.~ 000 00 g O 0 ~) ~D N ~ O 0 ~D 0 ~:1 h ~1 I o 3 . N O~ o 8 N N O

N U~ N O

o -- ~
U~

a ~ ~ 3 Le A 16 565 -57-. .

108{~230 a~
~: h _ _ _ D~ 00~ ooa~ o~ oo O O
O
El h o g .,1 .,_1 P ~
~ a~ ~
3 0 ~ .
rl ~q O ~
0: ~ . ~ O O ~ O O ~ O ~ O
~ o~ ooo ooo oo oo q~ o o P t~

h ~0 0 ~
E~ 0 O
: _ _~

,_ _~
a) o o _ N t~ ~0 N _ ~

S

~ b~3O~
P ~
~ ~ ~, V ~, ~e A 16 565 -58 -108o23o _ U~
a~
_ ~o ~ O O 0 O ~ O ~U
~ ~a ~ ~
o o 0~
~ o ', I o h a, a .
g a ~ ~

a ¦ ~ rl N O O ~J O O N O
~ ~1 o~o I 00 E-l 0 'q O ~
P~
O

O
0~

O t ~

Ul G ~3 ~" 0--~-~

Ie A 16 565 - 5~ -. ~ ~

_ '~ ~
a m _ _ _ _ _ ,~ ~h O ~O O a) O O ~ O N O O a~
O O ~ _ O
E~ ~
,~ o h c~ ~
g - ~ ~ J O t~J o N N
O r~ t~J ON O O ~U O N O ~ 0 8 _ ~ o~ .. ... ... .. ~
~ o~o ooooo ooo oo ooo o~ :~ o m O ~

_ _ _ _ _ O

D
\/
D~
~ \ D 8 D ~D 8~ ~
O ~ O c5 o o ~ ¦ D D D ~ D

L~ A 16 565 _60 108~)Z30 -~ _ .3 ~
~ U~
g ~ _ _ o _ o _ o _ O o O

t:l h O
.

~
_~
~ 0 r~ o.
o~ a~ o o ~ ., ._ ~ 0 0 0 ~08 ~0 ~0 ~o ~0 ~1 ~ ~ 000 00 oo oo 00 ~ O 0~
~ q~ ~ O
E~ ~0 ô~

,,~

~ ~ O ~ \ / O
~ ~ ~

~e A 16 565 -61 _ fi~
~ ~ 0 oo0 oo0 o oo~
oo ~o ~O~ . ~O.D _ ~ _ ~O
h O

^ O

h N O O N O N O O
C o o o o o o o o o o o ~1~ 3~

_~
~_ _ ~ ~ C~

o o ~\, / \ / ~ ~ ~ o 3~ ¢~ o~

~e A 16 565 _62 _ ^ ~j O ~o O o ~ o 0o o o o ~q o ~ C~ ~o~
O~d O ~
a ~ ~ ,1 ~ o ~ o ~ o 8 ~o~ oo oo ooo ~ ~ o ~ _ o_ ~ ~ 8~

.) H

~e A 16 565 _63, _ 1080Z3~

E~amPle ~ o IDloo test Test insect~: SitoPhilus r~nariue Solvent: Acetone 2 parts by weight oi the active compound were taken up in 1,000 parts by volume of the solvent. The solution 80 obtalned was diluted with further solvent to the desired concentrations.
2.5 ml oi the solution oi the active compound were pipetted into a Petri dish. On the bottom oi the Petri dish there was a iilter paper with a diameter oi about 9.5 cm. The Petri dish remained uncovered until the ~olvent had completely evaporated. The amount of active compound per m oi iilter paper varied with the concentration oi the solution oi active compound. About 25 te~t insects were then placed in the Petri dish and it was covered with a glass lid.
The condition oi the test insects wae obsorved 3 days aiter the commencement oi the esperiments. ~he destruction, in ~, was determined. 100% denotee that all oi the teet ineecte had besn killed; 0% denotes that no test insecte had been killed.
The active compounds, the conce~tratlone oi the active compounds, the test in~ects and the results c~n be eeen irom the iollowlng table:

~e ~ 16 565 - 64 -,~, h ~q o g8 h~ o o _ P~ _ o O o u~
~ .~

_ ~d .I C ~1 ~ Rc~ O ~10 ~ O O ~J O ~10 0 ,, C ~ C~ 0 0 0 0 0 0 0 0 0 0 0 0 E~l K C O

'~ g 1~ J

~ntsPI U"

,~ W,~

~eA 16 565 -65 .

o a) q~ ooo oo oo oo oo o ooo oo oo oo oo a~ _~
o~

g ,, -- h ~ a~
0~ ~
O~ ~ o ~J N N C~l O '1 ~ ~U O CU O N O C~l O ~J O
~ ~ ~ o o o o o o o o o o o ~ O

E~ ~ 0 ~8 ,~ ~
o a~ r-~D N ~ C~

c~N

~e A 16 565 - 66 -o ~1 h a~

~0 O O
88 o8 80 gog 888 __ __ ~ ___ ~__ .~ h~
~ ,~

o I ~
t~ ~ h O ~ o ~ N O O ~ ~
_l ~ - - ~ . - - -g 00 00 000000 _ o ~,CU

O U I ` U

~r:

~e A 16 565 - 67 -, o O 00 00 OOU~00 000 __ __ __ __ ___ a~
&~
a o a ~ h O ~

o ~ O 1N O N O ~J O O o ~ 0 8 o ,~ 07 oo oo ooo ooo ,1 ~: ~

o ~ "~
8~ 3"
~ ~ ~ ~ o O D D D

~e A 16 565 - 68_ 1080'Z30 .

U~
G~ 00 0 00 o o oo o a- o o O O O O
o , C~
C>
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O V) ra ~
N N
~,1 O ~ N, N ON O N
O rC ~ S N O N O O N O O N O
~ o o o o o o o' o o o' O
v~ ~
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~d ~ ¢ ~0 E- a ~_ ., ~ _I~ ~

o ~1 o I~ ~ In rl 3 ~ t-7 ~ N 1 c~ O
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E ~ 0 .
:.

1()80Z30 o h ~a ~o 8 8 8 8 8 o o o o o 8 U) b Q r~

,_ _ o a> 0 ., ~ h h a ~ ~
o ~
0 o ~
~1 ~1 ~ O N N N N N N
O ~ N O N O N O N O N O N O
~:~ 0'0 00 00 00 00 00 td ~: oo a~
E-~ o~
~ O Q~
8 ~ o ~

N N t-- 0 _ _ _ O _ U~

N 11~ C~ N ¦~ \ /
O~ ~ O ~

~e A 16 565 _70 -~080Z30 The procee~ of thls lnventlon i~ llluatrated by the followlnB preparativ~ E~cample~.
Exam~le 1~1:

Cl~ ; ~C2~5 ~ ~ C H

26,1 g (0.15 mole) o~ 0-ethyl-thionoethanepho~phonic acid e~ter chloride were added dropwise to a micture Or 19.5 g (0.15 mole) of 3-chloro-1,6-dihydro-6-oso-pyrldazlne and 21.4 g (0.155 mole) of pota~lum carbonate in 150 ml of acetonitrile. The mlxture wa~ warmed to 40C ~or throe houre and was then ~lltered, and the illtrate was poured into 200 ml of toluene. The toluene ~olutlon wae washed with saturated eodium carbonate solutlon and water, drled o~er sodlum ~ulfate and then concentrated. Thie gavo 34 g (85% oi theory) o~ 0-ethyl-0-[6-chloro-pyrldazln(3)gl]-eth~Lnethlonophosphonlc acid eeter ln the i~orm o~ colorle~
cry~tals OI meltlng point 58C.
E~amle 12:

CH30-e~ S ~oc3H7-l-o A mi~ture oi 16.4 B (0.1 mole) oi the potasslum derl~ratl~o OI 6-metho~y-3-hydro~y-pyridazi~e, 17.3 g (0.1 mole) o~ 0-iaopropyl-thionomethanephospho~ic acid eetor chloride a~ld 200 ml of acetonitrlle was ~tirred ior 3 hours at 50C. ~ter addinB 300 ml oi tolu~n~, the raaction misture wae washed twlce wlth 200 ml o~ water at a tim~ and wae drled o~er 8ulfate and the aol~ont vas dietillod oi~

~e A 16 565 _ 71_ in vacuo. 19.8 g (76% oi theory) oi 0-isopropyl-0-~6-methoxy-pyridazin(3)yl]-thionomethanepho~phonic acld e~ter were thu~ obtained in the form o~ a colorless powder o~
melting point 61C.
E~am~le 13:

CH -NH-Co-o- ~
3 ~-w CH3 (3)

6.3 g (0.11 mole) oi ~ethyl ieocyanate were added dropwise at 20-30C to a ~olution oi 24.6 g (0.1 mole) oi 0-isopropyl-0-[6-hydroxy-pyridazin(~)yl]-thionometbane-; 10 phosphonic acid ester and 0.2 B oi diazabicyclooctane in 200 ml oi methylene chloride. The mixture was stirred ior a further 18 hour~ at room temperature and then iiltered.
Aiter evaporating ofi the solvent, 28 g (92% oi theory) oi 0-lsopropyl-0-[6-N-methylcarbamoylo~y-pyridazin(3)yl]-thionomethanephosphonic acid ester remained in the iorm oi colorless crystals oi melting point 73C.
Esqm~le ~4:
(a) 1,6-Dihydro-3-methylsu1fonyloxy-6-oxo-pyridazine required as a starting material was prepared as ~ollows:

'' ~ Le A 16 565 -7~-1~80Z30 CH 3 S02 ~?
H
102,9 g (0.9 mole) of methanesulfonic acid chloride were added dropwise at 0C to a solution o~ 100.8 g (0.9 mole) of l,6-dihydro~ypyridazlne and 50.4 g (0.9 mole) oi potassium hydroxlde in 500 ml of water. The mixture WaB
allowed to react for a further hour at 20C and was then cooled to -10C, and the precipitate formed wae ~iltered off. After recrystallization from acetonltrile, 87 g (51%
of theory) of 1,6-dihydro-~-methylsulfonyloxy-6;oxo-pyridazine were obtained in the form o~ colorless crystals of melting point 148C.
(b) CH -S0 -0- ~ -0-P
3 2 NS C~3 (4) 9.5 g (50 m mcles)of 0-[6-hydro~y-pyrldazln(3)yl]-methanesulphonlc acid ester, 8.5 g ~5m moles) of ground potaeelum cPrbonate and 100 ml oi acetonitrllo were heated to 50C whll~ etirring and lmm0diately aiterwards were cooled to 30C, and 7.9 g (50 mmolee) oi 0-ethyl-methanethiono-phosphonic acid eeter chloride were added. ~he mi~ture was atirred ior a iurther ~0 minutee at room temperature and then ior 1 hour at 50C, and Wa8 iiltered; the iiltrate wae evaporated in ~aGUO. ~he reeidue wae shaken with 100 ml oi Le A 16 565 _73_ toluene and the organic phaee wa~ decanted off the ~ediment, wa~hed with 25 ml of water, drled o~er magneslum ~ulfate and worked up in the uaual manner. The ~olid whlch remained was wa~hed with 25 ml o~ ether. 9 g (60% of theory) Or 0-ethyl-0-~6- methylsulfonyloxy-pyridazin(3)yl~ -thiono-methanephosphonlc acid ester were obtalned ln the form colorles~ powder of melting polnt 110-120C.
ExamPle 1~:

~3-co-o-~ S ~ OC2H5 14.0 g (0.1 mole) of benzoyl chlorlde were added drop-wise at 24,8 8 (0.1 mole) oi 0-ethyl-0-[6-hydro~y-pyrldazin (3)yl]-thionoethanepho~phonic acid ester, 200 ml of methylene chloride and 10.1 g (0.1 mole) Or triethylamine at between 20 and 30C, whi1e stirring. The mi~ture wae then stlrred ror a further 2 hours at room temperature, the reactlon solution wa~ estracted by shaklng twice w~th 100 ml o~ water at a time and the organic phase was drled o~er magnesium ~ulfate and worked up in the usual manner. 27.5 g (78% of theory) oi 0-ethyl-0-[6-benzoylo~y-pyridazin(3)yl~-thionoethanephosphonic acid e~ter remained ln the iorm oi a light yellow oil oi reiracti~e lnde~ ~1 1.5610.
The iollowing compounde Or the general iormula P 0 ~ 3 (I) were prepared an~logously to one o~ E~a~pleg 11-15, Compounds 17, 18, 19 and 21 are, in each case, i80mer mixtures.
~e A 16 565 _ 74 _ ~ ., ,1 o _q~
~d h ~ N
-- p",.~ 0 N
~0 O u~ N ~ ~ N ~ 0 ~ P~ ~ O C ~ ~ ~
-h ,~ J 0~ 0 0 u~

O ~ 0~
oN (~

.: c~ m m c~ v o c~ ~

P: ~ V ~ N c~N
5:~
O O C~ O
1 ''I , ' ~ ~N r~
:r; ~ 5: N ~ N ~ N ~ N N

O O O O O , O O u~ Q O O

0 ~ ,~

b 3 , lO~OZ30 K

~ .~ ~
h ~ ~

_ q~ N o ~ C~ O o ._ ~ ~ ~ h t~ O
~0 to ~ O O 1 P,~rl N ~:1 N ~ N C~ ~ N Q ~ C~ ~ N ~ t~J
1~ ~ a a a n, ~ ~ a a a~D a lR~ ~` O O J 11~ t` ~1 ~ ~I N r-l ;t ~ ~ u~ ou~
~ ~ I~

~I r ~ 1 ~3 ~

N ~ C~N ~ C~N 3~ U

3 a 3 3 ~ o o o o o o o o o o o~ o O ~ N 1~
,~ ~I rt N N N N N N N N ~;i ~ .

I~ A 16565 _ 76 -o ,.

~080Z30 ,, o _~ o o o o o o o o o o o 'd h ~ 0~ ~ ~ N 0~ N ~ O ~4 O~ O ~ N

O
.. .. .. .- - - - - ~` CO - - -O ~ ~J a N 1:~ N C~ N ~Nl ~ N ~ N ~ ~ 0 N ~ ~ l l ~'0 ~ C
~P.

~1 o o ~ o 0 a~ CD O U~ O
0 a~ 0 0 u~

1: X X X

N ~N IN IN ~N

P~ ~ ~N ~ N

O O O O O O O
a ~ oo o P-- ~; N ~ N
l l l l l l l l l I
~ o o o o ~ o o ~,q o o u~ o o O~ O r~l N 1~ t~ ~ t~ O ~1 N ~ ~ ~ r ~
~

Ilfl A 16 565 _ 77 _ ~080230 ~d ~ ~O J
~0 _U"~
C) ' ~ 0 ~ r-l N ~ r~l C~ .. .. I I ~ I - - I
m ~ NC~JN~ N U~ N ~ ~ N~ i~
~-0 ~ 1 C ~ ~1 .

. X

l ~ol~ ~ ol oq O.

:~
~ o o o o c~ o o o o ~q ~ ~ u~ ~ ~ ~ ~

~ ~ o A 16 565 -78` _ ... ~ . ~

V--o td 0 0 U~
,~ o o ,~
rl t )~ _l ~ O ~ O O
~ ~, ~ ~ ~ o~ .
c~- ~d ~ I I I ~
~ h O u~ ~ a a~ ~
~1 o~ ~ w ~3 h __ ,_ N
0 o ~ 0;~, 0 0, 0 ~ X
~ ~ t Z Z Z
U~ U~

~;
1a ~; ~ V C~ C~
~ O O O O O O O

O ~ ~ ,~

~ ~ 16 565 - 79-., ,, )Z30 Other compounds which can be Yimilarly prepared include:
Compound X Y Rl R2 R3 R4 59 o O -C2H5 -C3H7-n~ CO-O- H

S O -C2H5 -C2H5 C2H5-NH-CO-O- }~

61 O O -C2H5 C2H5 CH3SO2 ~ O- H

62 O O -C2H5 -C2H5 ClCH2S2 ~ O- H
63 s n -C2H5 -C2H5 C~30- H
and the like.

Le A 16 565 -80-1081)230 It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of S the pre6ent lnvention.

LR A 16 565 -81- , ~, ,~

Claims (10)

What we claim is:

1. An O-[6-substituted-pyridazin(3)yl]-(thiono) (thiol)alkanephosphonic acid ester of the formula in which X and Y each independently is oxygen or sulfur, R1 is alkyl with 1 to 6 carbon atoms, R2 is alkyl with 1 to 4 carbon atoms, R3 is alkoxy with 1 to 4 carbon atoms, alkynyloxy with 2 to 5 carbon atoms, alkylsulfonyl-oxy with 1 to 3 carbon atoms, monoalkylcarbamoyloxy with 1 to 3 carbon atoms, halogen, benzyloxy, benzoyloxy, phenoxy, or phenoxy carrying at least one substituent selected from halogen, nitro, cyano, -SO2CH3, -SO2CH2Cl, and alkyl, halogenalkyl or alkylthio, each with up to 3 carbon atoms, and R4 is hydrogen or alkyl with 1 to 3 carbon atoms.

2. An ester according to claim 1, in which X is sulfur, Y is oxygen, R1 is alkyl with 1 to 5 carbon atoms, R2 is alkyl with 1 to 3 carbon atoms, R3 is alkoxy with 1 to 3 carbon atoms, alkynyloxy with 3 or 4 carbon atoms, chlorine, bromine methylsulfonyloxy, ethylsulfonyloxy, N-methyl-carbamoyloxy, N-ethylcarbamoyloxy, benzoyloxy, benzyloxy, phenyloxy, or phenyloxy carrying up to three substituents selected from chlorine, nitro, cyano, methyl, ethyl, methylthio, ethylthio and trifluoromethyl, and R4 is hydrogen, methyl or ethyl.

3. O-Isobutyl-O-[6-chloro-pyridazin(3)yl]-thionoethanephosphonic acid ester of the formula

4. O-Isopropyl-O-[6-ethoxy-pyridazin(3)yl]-thionoethanephosphonic acid ester of the formula

5. O-Methyl-O-[6-ethoxy-pyridazin(3)yl]-thionoethanephosphonic acid ester of the formula

6. 0-Methyl-O-[6-methylsulfonyloxy-pyridazin(3)yl]-thionoethane-phosphonic acid ester of the formula

7. O-Isopropyl-O-[6-(2',4'-dichlorophenoxy)-pyridazin-(3)yl]-thiono-methanephosphonic acid ester of the formula

8. A method of combatting insects, acarids, nematodes or fungi which comprises applying to the insects, acarids, nematodes or fungi, or to a habitat thereof, an insecticidally, acaricidally, nematocidally or fungicidally effective amount of a compound according to claim 1.

9. A method of combatting insects, acarids, nematodes or fungi which comprises applying to the insects, acarids, nematodes or fungi, or to a habitat thereof, an insecticidally, acaricidally, nematicidally or fungicidally effective amount of a compound according to claim 2, 3 or 4.

10. A method of combatting insects, acarids, nematodes or fungi which comprises applying to the insects, acarids, nematodes or fungi, or to a habitat thereof, an insecticidally, acaricidally, nematicidally or fungicidally effective amount of a compound according to claim 5, 6 or 7.